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Sintering and Mechanical Properties of Magnesium and Fluorine Co-Substituted Hydroxyapatites

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DOI: 10.4236/jbnb.2013.41001    3,863 Downloads   6,395 Views   Citations


Biological apatites contain several elements as traces. In this work, Magnesium and fluorine co-substituted hydroxyapatites with the general formula Ca9Mg(PO4)6(OH)2-yFy, where y = 0, 0.5, 1, 1.5 and 2 were synthesized by the hydrothermal method. After calcination at 500℃, the samples were pressureless sintered between 950℃ and 1250℃. The substitution of F- for OH- had a strong influence on the densification behavior and mechanical properties of the materials. Below 1200℃, the density steeply decreased for y = 0.5 sample. XRD analysis revealed that compared to hydroxylfluorapatite containing no magnesium, the substituted hydroxyfluorapatites decomposed, and the nature of the decomposition products is tightly dependent on the fluorine content. The hardness, elastic modulus and fracture toughness of these materials were investigated by Vickers’s hardness testing. The highest values were 622 ± 4 GPa, 181 ± 1 GPa and 1.85 ± 0.06 MPa.m1/2, respectively.

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S. Nsar, A. Hassine and K. Bouzouita, "Sintering and Mechanical Properties of Magnesium and Fluorine Co-Substituted Hydroxyapatites," Journal of Biomaterials and Nanobiotechnology, Vol. 4 No. 1, 2013, pp. 1-11. doi: 10.4236/jbnb.2013.41001.


[1] S. V. Dorozhkin, “Bioceramics of Calcium Orthophosphates,” Biomaterials, Vol. 31, No. 7, 2010, pp. 1465-1485. doi:10.1016/j.biomaterials.2009.11.050
[2] E. Landi, S. Sprio, M. Sandri, G. Celotti and A. Tampieri, “Development of Sr and CO3 Co-Substituted Hydroxyapatites for Biomedical Applications,” Acta Biomaterialia, Vol. 4, No. 3, 2007, pp. 656-663. doi:10.1016/j.actbio.2007.10.010
[3] M. E. Fleet, X. Liu and X. Wang, “Magnesium Carbonate-Phosphate Glass,” Journal of Non-Crystalline Solids, Vol. 355, No. 52-54, 2009, pp. 2604-2609. doi:10.1016/j.jnoncrysol.2009.09.006
[4] R. Z. LeGeros, “Apatites in Biological Systems,” Progress in Cryatal Growth Characterization of Materials, Vol. 4, No. 1-2, 1981, pp. 1-45. doi:10.1016/0146-3535(81)90046-0
[5] C. Capuccini, P. Torricelli, F. Sima, E. Boanini, C. Ristoscu, B. Bracci, G. Socol, M. Fini, I. N. Mihailescu and A. Bigi, “Strontium-Substituted Hydroxyapatite Coatings Synthesized by Pulsed-Laser Deposition: In Vitro Osteoblast and Osteoclast Response,” Acta Biomaterialia, Vol. 4, No. 6, 2008, pp. 1885-1893. doi:10.1016/j.actbio.2008.05.005
[6] B. Bracci, P. Torricelli, S. Panzavolta, E. Boanini, R. Giardino and A. Bigi, “Effect of Mg2+, Sr2+, and Mn2+ on the Chemico-Physical and in Vitro Biological Properties of Calcium Phosphate Biomimetic Coatings,” Journal of Inorganic Biochemistry, Vol. 103, No. 12, 2009, pp. 1666-1674. doi:10.1016/j.jinorgbio.2009.09.009
[7] J. F. McClendon, W. C. Foster and N. V. Ludwick, “Prevention of Dental Caries by Brushing the Teeth with Powders Containing Fluorapatite,” Journal of Dental Research, Vol. 26, No. 3, 1947, pp. 233-239. doi:10.1177/00220345470260030601
[8] M. Sundfeldt, M. Widmark, A. Wennerberg, J. K?rrholm, C. B. Johansson and L. V. Carlsson, “Does Sodium Fluoride in Bone Cement Affect Implant Fixation? Part I: Bone Tissue Response, Implant Fixation and Histology in Nine Rabbits,” Journal of Materials Science: Materials in Medicine, Vol. 13, No. 11, 2002, pp. 1037-1043. doi:10.1023/A:1020336404407
[9] M. Sundfeldt, J. Persson, J. Swanpalmer, A. Wennerberg, J. K?rrholm, C. B. Johansson and L. V. Carlsson, “Does Sodium Fluoride in Bone Cement Affect Implant Fixation Part II: Evaluation of the Effect of Sodium Fluoride Additions to Acrylic Bone Cement and the Fixation of Titanium Implants in Ovariectomized Rabbits,” Journal of Materials Science: Materials in Medicine, Vol. 13, No. 11, 2002, pp. 1045-1050. doi:10.1023/A:1020340521246
[10] H. Qu and M. Wei, “The Effect of Fluoride Contents in Fluoridated Hydroxyapatite on Osteoblast Behavior,” Acta Biomaterialia, Vol. 2, No. 1, 2006, pp. 113-119. doi:10.1016/j.actbio.2005.09.003
[11] K. A. Bhadang, C. A. Holding, H. Thissen, K. M. McLean, J. S. Forsythe and D. R. Haynes, “Biological Responses of Human Osteoblasts and Osteoclasts to Flame-Sprayed Coatings of Hydroxyapatite and Fluorapatite Blends,” Acta Biomaterialia, Vol. 6, No. 4, 2010, pp. 1575-1583. doi:10.1016/j.actbio.2009.10.029
[12] S. M. Barinov, S. V. Tumanov, I. V. Fadeeva and V. Yu. Bibikov, “Environment Effect on the Strength of Hydroxy- and Fluorohydroxyapatite Ceramics,” Journal of Inorganic Materials, Vol. 39, No. 8, 2003, pp. 877-780. doi:10.1023/A:1025041817017
[13] P. Spencer, C. Barnes, J. Martini, R. Garcia, C. Elliott and R. Doremus, “Magnesium Distribution in Human Bone,” Archives of Oral Biology, Vol. 34, No. 10, 1989, pp. 767-771. doi:10.1016/0003-9969(89)90026-5
[14] L. N. Y. Wu, B. R. Genge and R. E. Wuthier, “Differential Effects of Zinc and Magnesium Ions on Mineralization Activity of Phosphatidylserine Calcium Phosphate Complexes,” Journal of Inorganic Biochemistry, Vol. 103, No. 7, 2009, pp. 948-962. doi:10.1016/j.jinorgbio.2009.04.004
[15] R. K. Rude, “Cause of Heterogenous Disease in Humans,” Journal of Bone and Mineral Research, Vol. 13, No. 4, 1998, pp. 749-758. doi:10.1359/jbmr.1998.13.4.749
[16] E. Landi, A. Tampieri, M. Mattioli-Belmonte, G. Celotti, M. Sandri, A. Gigante, P. Fava and G. Biagini, “Biomimetic Mg- and Mg,CO3-Substituted Hydroxyapatites: Synthesis Characterization and in Vitro Behaviour,” Journal of European Ceramic Society, Vol. 26, No. 13, 2006, pp. 2593-2601. doi:10.1016/j.jeurceramsoc.2005.06.040
[17] G. Qi, S. Zhang, K. A. Khor, S. W. Lye, X. Zeng, W. Weng, C. Liu, S. S. Venkatraman and L. L. Ma, “Osteoblastic Cell Response on Magnesium-Incorporated Apatite Coatings,” Applied Surface Science, Vol. 255, No. 2, 2008, pp. 304-307. doi:10.1016/j.apsusc.2008.06.106
[18] S. Kannan, I. A. F. Lemos, J. H. G. Rocha and J. M. F. Ferreira, “Synthesis and Characterization of Magnesium Substituted Biphasic Mixtures of Controlled Hydroxya-patite/β-Tricalcium Phosphate Ratios,” Journal of Solid State Chemistry, Vol. 178, No. 10, 2005, pp. 3190-3196. doi:10.1016/j.jssc.2005.08.003
[19] W. L. Suchanek, K. Byrappa, P. Shuk, R. E. Riman, V. F. Janas and K. S. TenHuisen, “Preparation of Magnesium-Substituted Hydroxyapatite Powders by the Mechanochemical-Hydrothermal Method,” Biomaterials, Vol. 25, No. 19, 2004, pp. 4647-4657. doi:10.1016/j.biomaterials.2003.12.008
[20] A. Bigi, G. Falini, E. Foresti, A. Ripamonti, M. Gazzano and N. Roveri, “Magnesium Influence on Hydroxyapatite Crystallization,” Journal of Inorganic Biochemistry, Vol. 49, No. 1, 1993, pp. 69-78. doi:10.1016/0162-0134(93)80049-F
[21] M. Okazaki, “Crystallographic Properties of Heterogeneous Mg-Containing Fluoridated Apatites Synthesized with a Two-Step Suphly System,” Biomaterials, Vol. 16, No. 9, 1995, pp. 703-707. doi:10.1016/0142-9612(95)99698-L
[22] Y. Cai, S. Zhang, X. Zeng, Y. Wang, M. Qian and W. Weng, “Improvement of Bioactivity with Magnesium and Fluorine Ions Incorporated Hydroxyapatite Coatings via Sol-Gel Deposition on Ti6Al4V Alloys,” Thin Solid Films, Vol. 517, No. 17, 2009, pp. 5347-5351. doi:10.1016/j.tsf.2009.03.071
[23] A. Gee and V. R. Deitz, “Determination of Phosphates by Differential Spectrometric,” Annales de Chemie, Vol. 25, No. 9, 1953, pp. 1320-1324. doi:10.1021/ac60081a006
[24] G. Charlot, “Méthodes de la Chimie Analytique: Analyse Quantitative Minérale,” Masson, Paris, 1966, p. 551.
[25] ASTM, “E384-99: A Standard Test Method for Microindentation Hardness of Materials,” ASTM, Philadelphia, 1984.
[26] D. B. Marshall, T. Noma and A. G. Evans, “A Simple Method for Determining Elastic-Modulus to Hardness Ratios Using Knoop Indentation Methods,” Journal of the American Ceramic Society, Vol. 65, No. 10, 1982, pp. C175-C176. doi:10.1111/j.1151-2916.1982.tb10357.x
[27] Z. Li, A. Ghosh, A. S. Kobayashi and R. C. Bradt, “Indentation Fracture Toughness of Sintered Silicon Carbide in the Palmqvist Crack Regimes,” Journal of the American Ceramic Society, Vol. 72, No. 6, 1989, pp. 904-911. doi:10.1111/j.1151-2916.1989.tb06242.x
[28] J. Gong, J. Wang and Z. Guan, “A Comparison between Knoop and Vickers Hardness of Silicon Nitride Ceramics,” Material Letter, Vol. 56, No. 6, 2002, pp. 941-944. doi:10.1016/S0167-577X(02)00641-9
[29] R. D. Shannon, “Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides,” Acta Crystallographica, Vol. A32, 1976, pp. 751-767.
[30] M. J. Larsen and S. J. Jensen, “Solubility, Unit Cell Dimensions and Crystallinity of Fluoridated Human Dental Enamel,” Archives of Oral Biology, Vol. 34, No. 12, 1989, pp. 969-973. doi:10.1016/0003-9969(89)90054-X
[31] M. Okazaki, “Fluoridated Hydroxyapatites Synthesized with Organic Phosphate Ester,” Biomaterials, Vol. 12, No. 1, 1991, pp. 46-49. doi:10.1016/0142-9612(91)90131-S
[32] L. M. Rodríguez-Lorenzo, J. N. Hart and K. A. Gross, “Influence of Fluorine in the Synthesis of Apatites. Synthesis of Solid Solutions of Hydroxy-Fluorapatite,” Biomaterials, Vol. 24, No. 21, 2003, pp. 3777-3785. doi:10.1016/S0142-9612(03)00259-X
[33] Y. Chen and X. Miao, “Thermal and Chemical Stability of Fluorohydroxyapatite Ceramics with Different Fluorine Contents,” Biomaterials, Vol. 26, No. 11, 2005, pp. 1205-1210. doi:10.1016/j.biomaterials.2004.04.027
[34] P. Hartmann, C. J?ger, St. Barth, J. Vogel and K. Meyer, “Solid State NMR, X-Ray Diffraction, and Infrared Characterization of Local Structure in Heat-Treated Oxyhydroxyapatite Microcrystals: An Analog of the Thermal Decomposition of Hydroxyapatite during Plasma-Spray Procedure,” Journal of Solid State Chemistry, Vol. 160, No. 2, 2001, pp. 460-468. doi:10.1006/jssc.2001.9274
[35] N. Senamaud, D. Bemache-Assollant, E. Champion, M. Heughebaert and C. Rey, “Calcination and Sintering of Hydroxyfluorapatite Powders,” Solid State Ionics, Vol. 101-103, 1997, pp. 1357-1362. doi:10.1016/S0167-2738(97)00242-7
[36] L. M. Rodríguez-Lorenzo, J. N. Hart and K. A. Gross, “Influence of Fluorine in the Synthesis of Apatites. Synthesis of Solid Solutions of Hydroxy-Fluorapatite,” Biomaterials, Vol. 24, No. 21, 2003, pp. 3777-3785. doi:10.1016/S0142-9612(03)00259-X
[37] K. A. Gross and L. M. Rodríguez-Lorenzo, “Sintered Hydroxyfluorapatites. Part I: Sintering Ability of Precipitated Solid Solution Powders,” Biomaterials, Vol. 25, No. 7-8, 2004, pp. 1375-1384. doi:10.1016/S0142-9612(03)00565-9
[38] M. Hidouri, K. Bouzouita, F. Kooli and I. Khattech, “Thermal Behaviour of Magnesium-Containing Fluorapatite,” Materials Chemistry and Physics, Vol. 80, No. 2, 2003, pp. 496-505. doi:10.1016/S0254-0584(02)00553-9
[39] J. Marchi, A. C. S. Dantas, P. Greil, J. C. Bressiani, A. H. A. Bressiani and F. A. Müller, “Influence of Mg-Substitution on the Physicochemical Properties of Calcium Phosphate Powders,” Materials Research Bulletin, Vol. 42, No. 6, 2007, pp. 1040-1050. doi:10.1016/j.materresbull.2006.09.015
[40] I. Cacciotti, A. Bianco, M. Lombardi and L. Montanaro, “Mg-Substituted Hydroxyapatite Nanopowders: Synthesis, Thermal Stability and Sintering Behavior,” Journal of European Ceramic Society, Vol. 29, No. 14, 2009, pp. 2969-2978. doi:10.1016/j.jeurceramsoc.2009.04.038
[41] J. Rodríguez-Carvajal, “A Program for Rietveld Refinement and Pattern Matching Analysis,” Physica, Vol. B192, No. 1-2, 1993, pp. 55-69. doi:10.1016/0921-4526(93)90108-I
[42] E. D. Franz, “Fluorapatit Ca5F(PO4)3: Ein Modell Zur Synthese der Zahnhartsubstanz im System CaF2-Ca3(PO4)2,” Z Naturforschung, Vol. 38b, 1983, pp. 1037-1040.
[43] F. Ben Ayed, J. Bouaziz and K. Bouzouita, “Pressureless Sintering of Fuorapatite under Oxygen Atmosphere,” Journal of European Ceramic Society, Vol. 20, No. 8, 2000, pp. 1069-1076. doi:10.1016/S0955-2219(99)00272-1
[44] M. Hidouri, K. Bouzouita and N. Fattah, “Effect of Additives on the Densification and the Microstructure of Magnesium-Containing Fluorapatite,” Annales de Chimie: Science de Matériaux, Vol. 30, 2005, pp. 133-138. doi:10.3166/acsm.30.133-148
[45] K. A. Gross and K. A. Bhadang, “Sintered Hydroxyfluorapatites. Part II: Mechanical Properties of Solid Solutions Determined by Microindentation,” Biomaterials, Vol. 25, No. 7-8, 2004, pp. 1385-1394. doi:10.1016/S0142-9612(03)00636-7
[46] M. Hidouri, K. Boughzala, J. P. Lecompte and K. Bouzouita, “Sintering and Mechanical Properties of Magnesium-Containing Fluorapatite,” Comptes Rendus Physique, Vol. 10, No. 2-3, 2009, pp. 242-248. doi:10.1016/j.crhy.2009.04.001
[47] H. Eslami, M. Solati-Hashjin and M. Tahriri, “The Comparison of Powder Characteristics and Physicochemical, Mechanical and Biological Properties between Nanostructure Ceramics of Hydroxyapatite and Fluoridated Hydroxyapatite,” Materials Science and Engineering, Vol. Vol. C29, No. 4, 2009, pp. 1387-1398. doi:10.1016/j.msec.2008.10.033
[48] D. J. Clinton and R. Morrell, “Hardness Testing of Ceramic Materials,” Materiel Chemistry and Physics, Vol. 17, No. 5, 1987, pp. 461-473. doi:10.1016/0254-0584(87)90096-4
[49] R. W. Rice, C. C. Wu and F. Borchelt, “HardnessGrain-Size Relations in Ceramics,” Journal of the American Ceramic Society, Vol. 77, No. 10, 1994, pp. 2539-2553. doi:10.1111/j.1151-2916.1994.tb04641.x

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